DE112019003641T5 - RUGGED NICKEL-PLATED SHEET METAL - Google Patents

Abstract

A roughened, nickel-plated sheet metal with a roughened nickel layer as the outermost surface layer on at least one surface of a metal base material is provided, the brightness L * of the surface of the roughened nickel layer being 30 to 50, the degree of gloss of 85 ° of the surface of the roughened nickel layer being 1.5 to 50.

Description

TECHNICAL AREA

The present invention relates to a roughened, nickel-plated sheet metal with a roughened nickel layer as the outermost surface layer.

STATE OF THE ART

Conventionally, as a component constituting the battery or a component constituting the electronic-related equipment, a nickel-plated steel sheet is used. When such a nickel-plated steel sheet is bonded to other members, there is known a method of controlling the surface structure of the nickel-plated steel sheet in order to improve the adhesion.

For example, Patent Document 1 discloses a surface-treated steel sheet formed by forming a nickel plating layer having a microstructure adjusted to a particle density of 2 to 500 particles / µm ² and an average particle diameter of 0.05 to 0.7 µm on a steel sheet .

PATENT DOCUMENT

Patent Document 1: Japanese Patent No. 5885345

SUMMARY OF THE INVENTION

PROBLEM TO BE SOLVED BY THE INVENTION

In the surface-treated steel sheet disclosed in Patent Document 1, however, depending on the kind of the component to be bonded to the surface-treated steel sheet and the bonding method, the adhesiveness to other components may be insufficient, and further improvement of the adhesiveness has been demanded.

On the other hand, a method is also conceivable in which a nickel plating layer is formed by roughening plating in order to improve the adhesion with other components. However, the investigations by the inventors of the present invention have found that there is a problem that the adhesion of the roughened plating layer, which is itself formed by roughening plating on the base material, is lowered and thus the reliability is lowered in some cases.

It is an object of the present invention to provide a roughened nickel-plated sheet which has excellent adhesion to other components while maintaining good adhesion of a cladding layer to a base material.

MEANS TO SOLVE THE PROBLEM

As a result of intensive studies to achieve the above object, the inventors of the present invention have found that by controlling the brightness and gloss level of 85 ° of the surface of the roughened nickel layer to a certain area, it is possible to obtain a roughened nickel-plated sheet which exhibits excellent adhesion to other components while maintaining good adhesion of the clad layer to the base material, thereby completing the present invention.

In particular, according to the present invention, a roughened, nickel-plated sheet metal or nickel-plated sheet metal is provided with a roughened nickel layer as the outermost surface layer on at least one surface of a metal base material, wherein
the brightness L * of the surface of the roughened nickel layer is 30 to 50,
the gloss level of 85 ° of the surface of the roughened nickel layer is 1.5 to 50.

In the roughened, nickel-plated sheet according to the present invention, it is preferable that the metal base material is a metal sheet or a metal foil made of a kind of pure metal, selected from Fe, Cu, Al and Ni, or a metal sheet or metal foil made of an alloy containing a kind selected from Fe, Cu, Al and Ni.

In the roughened nickel-plated sheet according to the present invention, it is preferable that the metal base material is a steel sheet.

In the roughened nickel-plated sheet according to the present invention, it is preferable that the thickness of the metal base material is 0.01 to 2.0 mm.

In the roughened nickel-plated sheet according to the present invention, it is preferable that the deposition amount of the nickel-plating is 5.0 to 50.0 g / m ² .

In the roughened nickel-plated sheet according to the present invention, it is preferable that the roughened nickel layer has an arithmetic mean roughness Ra of 0.1 to 3.0 µm by laser microscopy and the roughened nickel layer has a ten-point mean roughness Rz _jis 2.0 to 20.0 µm by laser microscopy.

EFFECTS OF THE INVENTION

According to the present invention, there can be provided a roughened nickel-plated sheet which has excellent adhesion to other components while maintaining good adhesion of the clad layer to the base material.

Figure list

• 1A Fig. 13 is a configuration diagram of a roughened nickel-plated sheet according to the present embodiment.
• 1B Fig. 13 is a configuration diagram of a roughened nickel-plated sheet according to another embodiment.
• 2 Fig. 13 is a first schematic view for explaining an example of a method of manufacturing a roughened nickel-plated sheet according to the present embodiment.
• 3 Fig. 13 is a second schematic view for explaining an example of a method of manufacturing a roughened nickel-plated sheet according to the present embodiment.
• 4th Fig. 13 is a third schematic view for explaining an example of a method of manufacturing a roughened nickel-plated sheet according to the present embodiment.
• 5 (A) and 5 (B) are photographs obtained by observing a surface of a roughened, nickel-plated sheet of Example 28 with a scanning electron microscope (SEM or SEM), 5 (C) and 5 (D) are photographs obtained by observing a cross section of a roughened nickel-plated sheet of Example 28 with a scanning electron microscope (SEM or SEM).
• 6 (A) and 6 (B) are photographs obtained by observing a surface of a roughened nickel-plated sheet of Comparative Example 5 with a scanning electron microscope (SEM), 6 (C) and 6 (D) are photographs obtained by observing a cross section of a roughened nickel-plated sheet of Comparative Example 5 with a scanning electron microscope (SEM).
• 7 (A) and 7 (B) Fig. 13 are schematic diagrams showing an embodiment of a roughened nickel layer.
• 8 (A) to 8 (C) Fig. 13 are schematic diagrams showing an embodiment of a roughened nickel layer.
• 9 (A) to 9 (D) Fig. 13 are schematic diagrams showing an embodiment of a roughened nickel layer.
• 10 (A) to 10 (D) Fig. 13 are schematic diagrams showing an embodiment of a roughened nickel layer.
• 11 (A) to 11 (C) are scanning electron microscopy (SEM) images of a cross section of a roughened nickel layer.
• 12 (A) to 12 (C) are scanning electron microscopy (SEM) images of a cross section of a roughened nickel layer.
• 13 (A) and 13 (B) are scanning electron microscopy (SEM) images of a cross section of a roughened nickel layer.
• 14 (A) and 14 (B) are scanning electron microscopy (SEM) images of a cross section of a roughened nickel layer.
• 15th Fig. 13 is a diagram for explaining a method of determining a boundary between a metal substrate and an underlying nickel layer and a boundary between an underlying nickel layer and a roughened nickel layer in Examples and Comparative Examples.

DESCRIPTION OF THE EMBODIMENTS

1A Fig. 13 is a diagram showing a configuration of a roughened nickel-plated sheet 1 of the present embodiment shows. As in 1A shown is the roughened, nickel-plated sheet metal 1 of the present embodiment with a roughened nickel layer 12th as the outermost surface layer on a metal base material 11 educated. In the roughened nickel-plated sheet metal 1 according to the present embodiment has the roughened nickel layer 12th a brightness L * from 30 to 50 and a gloss level of 85 ° from 3 to 50.

In the present embodiment, as shown in 1A shown is the roughened nickel-plated sheet 1 , in which the roughened nickel layer 12th on both surfaces of the metal base material 11 is formed is illustrated, but it is not particularly limited to such an embodiment, and for example, the roughened nickel layer may 12th on a surface of the metal base material 11 be designed as in the 1B shown roughened nickel-plated sheet metal 1a .

<Metal Base Material 11>

The metal base material 11 as the substrate of the roughened nickel-plated sheet 1 The present embodiment is not particularly limited to a metal sheet or a metal foil made of one kind of pure metal selected from Fe, Cu, Al and Ni, or a metal sheet or a metal foil made of an alloy which is one kind selected from Fe, Cu, Al and Ni, particularly sheet steel, iron sheet, stainless steel sheet, copper sheet, aluminum sheet or nickel sheet (these can be any of the pure metals and alloys, can be a foil.) Among them, there is, as the plating also with a relatively simple pretreatment of the plating process is easy to carry out and it is easy to form a strongly adhering roughened nickel layer on the metal base material, a steel sheet or a copper sheet is preferred, in particular a low-carbon aluminum-killed steel (carbon content from 0.01 to 0.15% by weight), particularly low-carbon steel Steel with a carbon content of 0.01% by weight or less (preferably a carbon content t of 0.003 wt% or less) or aging-resistant high carbon steel made by adding Ti, Nb and the like to high carbon steel is preferably used.

In the present embodiment, a steel sheet, copper sheet, aluminum sheet or nickel sheet obtained by hot rolling any of these sheets, acid pickling the hot rolled sheet to remove scale (oxide film) on the surface, and cold rolling the pickled sheet can be used as the substrate. Alternatively, a sheet metal can be used on which annealing or rolling with tempering is carried out after electrolytic cleaning. In this case, the annealing may be continuous annealing or box annealing, which is not particularly limited. In addition, as the electrolytic foil produced by the electroforming method, copper foil, nickel foil, iron foil or the like can also be used as a metal base material.

• Badzusammensetzung: Nickelsulfat-Hexahydrat 100 bis 300 g/L, Schwefelsäure 10 bis 200 g/L
• pH-Wert: 1,0 oder weniger
• Badtemperatur: 40 bis 70°C
• Stromdichte: 5 bis 100 A/dm²
• Plattierungszeit: 3 bis 100 Sekunden

Incidentally, it is with the metal base material 11 , when using a metal base material in which a passive film is formed on the surface, such as a stainless steel sheet and a nickel sheet, before plating roughened nickel or before the plating process for forming the underlying metal plating, it is preferable to use those that have a Strike nickel plating. Impact nickel plating conditions are not particularly limited, and the following conditions may be established, for example. Under the following conditions, the deposition amount of nickel by impact nickel plating is normally 0.08 to 0.89 g / m ² , but when an underlying nickel layer is formed, the sum of the deposition amount of nickel becomes through Impact nickel plating and the amount of deposition of nickel by nickel plating to form an underlying nickel layer are measured as the amount of deposition of nickel by the underlying nickel layer.

• Bath composition: nickel sulfate hexahydrate 100 to 300 g / L, sulfuric acid 10 to 200 g / L
• pH value: 1.0 or less
• Bath temperature: 40 to 70 ° C
• Current density: 5 to 100 A / dm ²
• Plating time: 3 to 100 seconds

The thickness of the metal base material 11 is not particularly limited, but is preferably 0.01 to 2.0 mm, more preferably 0.025 to 1.6 mm, and even more preferably 0.025 to 0.3 mm. Further is the roughness of the metal base material 11 not particularly limited, but the arithmetic mean value of the roughness Ra in the pen-shaped surface roughness meter is 0.05 to 2.0 µm, more preferably 0.05 to 0.9 µm, and still more preferably 0.05 to 0.5 µm.

<Roughened nickel layer 12th >

The ones on the outermost surface of the roughened, nickel-plated sheet metal 1 the roughened nickel layer formed in the present embodiment 12th is one in which the brightness L * of the surface is controlled to 30 to 50 and a gloss level of 85 ° of the surface is controlled to 3 to 50. According to the present embodiment, by controlling the brightness L * and the gloss level of 85 ° of the surfaces of the roughened nickel layer 12th the roughened, nickel-plated sheet metal within the above ranges 1 as one that has excellent adhesion to other components while having good adhesion of the roughened nickel layer 12th on the metal base material 11 is retained.

In particular, as a result of intensive studies by the inventors of the present invention, the present inventors found the relationship between the lightness L * and the degree of gloss of 85 ° of the surface of the roughened nickel layer 12th and the adhesiveness of the roughened nickel layer 12th on the metal base material 11 and the adhesiveness of the roughened nickel layer 12th found on other components that by setting the brightness L * and the degree of gloss of 85 ° of the surface of the roughened nickel layer 12th the roughened nickel-plated sheet metal on the above areas 1 can have excellent adhesion to other components, while the adhesion of the roughened nickel layer 12th is well maintained, and the present invention has been completed.

According to the present embodiment, in addition to the excellent adhesion to other components, the adhesion of the roughened nickel layer is also important 12th to the metal base material 11 respected for the following reason. That is, through the formation of the roughened nickel layer 12th even if it is possible to exhibit excellent adhesiveness to other components when the roughened nickel layer 12th slightly from the metal base material 11 falls off, due to the fact that the roughened nickel layer 12th falls off, the effect due to the formation of the roughened nickel layer 12th becomes insufficient, that is, the effect in which it is possible to exhibit excellent adhesiveness to other components becomes insufficient. Therefore, from this point of view, the inventors of the present invention have the adhesion of the roughened nickel layer 12th on the metal base material 11 Paying attention and improving it.

In addition, when the adhesion of the roughened nickel layer 12th on the metal base material 11 is insufficient in the manufacture of the roughened nickel-plated sheet 1 In the present embodiment, the plating film residue (Ni powder) due to the falling off of the roughened nickel layer 12th mixed in the production line, in addition to causing contamination or breakdown of the production line, and there is a case where product defects are caused due to the cladding film residue left on the production line. In addition, the use of the roughened, nickel-plated sheet metal causes 1 According to the present embodiment, similarly, even if it is actually made into products or parts, contamination or failure of the production line, and there is a possibility that it may cause defects in the quality or function of the final product. Therefore, the inventors of the present invention paid attention to the importance of the adhesion of the roughened nickel layer from this point of view as well 12th on the metal base material 11 respected and improved it.

The brightness of the surface of the roughened nickel layer 12th is at a value of L * between 30 and 50, preferably between 30 and 48, more preferably between 30 and 45, and still more preferably between 35 and 45. From the viewpoint of emphasizing production efficiency and production cost it is preferable that the brightness of the surface of the roughened nickel layer 12th 36 to 48. If the value of the lightness L * is too small, the adhesion of the roughened nickel layer will decrease 12th on the metal base material 11 worse, while if the value of the brightness L * is too large, the adhesion to other components becomes worse. It should be noted that the lightness L * of the surface of the roughened nickel layer 12th can be measured with a spectrophotometer according to the SCE method (specular reflected light removing method) according to JIS Z8722.

The “glossiness” of 85 ° of the surface of the roughened nickel layer 12th is 1.5 to 50, preferably 1.5 to 35, and particularly preferably 2 to 30. From the viewpoint of emphasizing production efficiency and production cost, the degree of gloss is 85 ° of the surface of the roughened nickel layer 12th preferably 15 to 50. If the gloss level of 85 ° is too small, the adhesion of the roughened nickel layer will decrease 12th on the metal base material 11 worse. If the gloss level is too high, the adhesion to other components will be poorer. It should be noted that the gloss level of 85 ° of the surface of the roughened nickel layer 12th can be determined by measuring the specular gloss of 85 ° with a gloss meter according to JIS Z8741. Incidentally, the gloss level of the roughened nickel layer is 60 ° 12th on the outermost surface of the roughened nickel-plated sheet 1 of the present embodiment is typically 10 or less.

Although the color value a *, b * of the surface of the roughened nickel layer 12th is not particularly limited, the color value a * is preferably 0.1 to 3.0, more preferably 0.3 to 1.5, and the color value b * is preferably 1.0 to 8.0, more preferably 2.0 to 7, 0, from the viewpoint that the adhesion of the roughened nickel layer 12th on the metal base material 11 and the adhesion of the roughened nickel layer 12th can be further improved on other components.

The roughened nickel layer 12th may have the lightness L * of the surface and the degree of gloss of 85 ° of the surface within the above ranges, but the arithmetic mean roughness Ra is preferably 0.1 to 3 µm from the viewpoint of improving the adhesion of the roughened nickel layer 12th on other members, the arithmetic mean roughness Ra is more preferably 0.18 µm or more, more preferably 0.3 µm or more, and from the viewpoint of improving the adhesion (plating adhesion) of the roughened nickel layer 12th on the metal base material 11 The arithmetic mean roughness Ra is more preferably 1.8 µm or less, still more preferably 1.6 µm or less, still more preferably 1.3 µm or less. Also, from the viewpoint of emphasizing production efficiency and production cost, the arithmetic mean roughness Ra is preferably 0.18 to 0.5 µm, more preferably 0.18 to 0.49 µm. The roughened nickel layer 12th preferably has a ten-point mean roughness Rz _jis of 2.0 to 20.0 µm from the viewpoint of further improving the adhesion of the roughened nickel layer 12th on other members, the ten-point average roughness Rz is _jis , more preferably 3 µm or more, still more preferably 4 µm or more, and still more preferably 5 µm or more, and from the viewpoint of further improving the adhesion (plating adhesion) of the roughened Nickel layer 12th on the metal base material 11 the ten-point mean roughness value Rz _{jis is more} preferably 16 µm or less, more preferably 14 µm or less, and still more preferably 12 µm or less. From the viewpoint of emphasizing production efficiency and production cost, it is preferable that the ten-point mean value of the roughness Rz _{jis is} 3.0 to 7.0 µm. It should be noted that the maximum height roughness Rz of the roughened nickel layer 12th is not particularly limited, but is preferably 2.5 to 25.0 µm, more preferably 2.5 to 20.0 µm, and still more preferably 3.5 to 18.0 µm. The surface roughness Ra, Rz _jis and Rz are preferably measured by means of laser microscopy.

The amount of deposition of the roughened nickel layer 12th in roughened nickel-plated sheet metal 1 of the present embodiment is not particularly limited, but is preferably 1.34 to 45.0 g / m ² , and from the viewpoint of further improving the adhesion (plating adhesion) of the roughened nickel layer 12th is the amount of deposition of the roughened nickel layer 12th more preferably 2.67 g / m ² or more, still more preferably 5 g / m ² or more, and from the viewpoint of further improving the adhesion of the roughened nickel layer 12th on other components the amount of deposition is the roughened nickel layer 12th more preferably 38.0 g / m ² or less, still more preferably 32.0 g / m ² or less, and even more preferably 31 g / m ² or less. The amount of deposition of the roughened nickel layer 12th can by measuring the total amount of nickel on the roughened, nickel-plated sheet 1 can be determined using a fluorescence x-ray machine. Incidentally, if an underlying metal plating layer 13th formed from nickel, which will be described later, after measuring the total amount of nickel using a fluorescent X-ray apparatus for the roughened nickel-plated sheet 1 can be determined by the amount of nickel present in the underlying metal plating layer 13th is deducted from the total amount of nickel. The amount of nickel contained in the underlying metal plating layer 13th for example, by a method of measuring the thickness of the underlying metal plating layer 13th by removing the roughened, nickel-plated sheet metal 1 cut and the cross section is observed with a scanning electron microscope (SEM or SEM), and then the amount of nickel is determined from the thickness of the underlying metal plating layer 13th is converted; a method of measuring the amount of nickel on the metal base material 11 at the time the underlying metal plating layer was formed 13th using a fluorescence x-ray machine; a method of determining the amount of electrodeposition calculated from the Coulomb amount in forming the underlying metal plating layer 13th by plating on the metal base material 11 and the like can be measured.

In the present embodiment, the method of adjusting the lightness is L * and the degree of gloss of 85 ° of the surface of the roughened nickel layer 12th not particularly limited in the above ranges, but a method for forming the roughened nickel layer 12th by the method described below or the like is exemplary.

An example of a method of forming the roughened nickel layer 12th will be referred to below with reference to 2 to 4th described. First, as in 2 shown from the viewpoint of further improving the adhesion between the metal base material 11 and the roughened nickel layer 12th and imparting corrosion resistance according to the application, an underlying metal plating layer 13th on the metal base material 11 formed as required. Although the roughened nickel layer 12th directly on the metal base material 11 can be formed without the underlying metal plating layer 13th To form, roughened nickel plating ("roughened nickel plating") is carried out next to the nickel grains 121 on the metal base material 11 to be deposited in an agglomerated state, as in FIG 3 shown. Next, as in 4th As shown, blanket nickel plating is performed around the nickel grains 121 with the nickel film 122 to plating, removing the roughened nickel layer 12th on the metal base material 11 is formed with the underlying metal plating layer 13th as required, is formed interposed therebetween.

The condition of plating roughened nickel to deposit the nickel grains 121 in an agglomerated state is not particularly limited, but from the viewpoint that the lightness L * and the degree of gloss of 85 ° of the surfaces of the roughened nickel layers 12th can be appropriately controlled within the above ranges, an electrolytic plating method using a plating bath containing nickel sulfate hexahydrate in a concentration of 10 to 100 g / L and ammonium sulfate in a concentration of 1 to 100 g / L is preferred. The concentration of nickel sulfate hexahydrate in the plating bath used is preferably 10 to 70 g / L, more preferably 10 to 50 g / L, and even more preferably 15 to 25 g / L. It should be noted that nickel chloride hexahydrate can be used as the source of nickel ions, or nickel chloride hexahydrate and nickel sulfate hexahydrate can be used in combination. When nickel chloride hexahydrate is used, the concentration of nickel chloride hexahydrate is preferably adjusted to 1 to 40 g / L. However, if the nickel ion concentration and the chloride ion concentration increase, it becomes difficult to obtain a suitable roughened shape having a predetermined brightness and gloss level, and therefore caution should be exercised in combining nickel sulfate hexahydrate and ammonium chloride. In addition, when ammonium sulfate is used as the ammonia source in the plating solution, the concentration of ammonium sulfate in the plating bath used is preferably 10 to 50 g / L, more preferably 10 to 45 g / L, and even more preferably 15 to 40 g / L. It should be noted that ammonia can be added to the nickel plating bath by adding ammonia water or by adding a salt such as ammonium sulfate and ammonium chloride. The concentration of ammonia in the plating bath is preferably 0.3 to 30 g / L, more preferably 1 to 20 g / L, even more preferably 3 to 15 g / L, and particularly preferably 3 to 12 g / L.

In addition, the pH of the nickel plating bath is preferably 4.0 to 8.0 when plating roughened nickel to precipitate the nickel grains 121 in an agglomerated state, from the point of view that the lightness L * and the degree of gloss of 85 ° of the surface of the roughened nickel layer 12th can be controlled more appropriately. If the pH is too high, the nickel ions in the bath tend to hydrate and cause plating failure, so the upper limit thereof is more preferably 7.5 or less, and still more preferably 7.0 or less. When the pH is low, the bath resistance is low and the nickel particles are less likely to precipitate in the state in which the secondary particles are formed, so that a normal precipitate shape (flat plating) is likely to be formed and it is difficult to obtain a roughened one Nickel layer, therefore, it is more preferably 4.5 or more, still more preferably 4.8 or more, and particularly preferably 5.0 or more.

The current density in performing the plating of roughened nickel to precipitate the nickel grains 121 in an agglomerated state is preferably 5 to 40 A / dm ² from the viewpoint that the lightness L * and the degree of gloss of 85 ° of the surface of the roughened nickel layer 12th can be controlled more appropriately. When the current density is high, the precipitation efficiency tends to be lowered, and plating unevenness and surface roughness control unevenness tend to occur in the area of plating treatment, so 30 A / dm ² or less is more preferable, more preferably 25 A / dm ² or less, and more preferably 20 A / dm ² or less, in order to secure particularly a large plating area of 100 cm ² or more. When the current density is low, the nickel particles are less likely to precipitate in the form of the secondary particles, and the nickel particles are more likely to be in the normal precipitate form, and therefore the roughened nickel layers are less likely to be formed. Therefore, it is preferable that the current density is 10 A / dm ² or more. In the present embodiment, it is from the viewpoint of controlling the lightness L * and the degree of gloss of 85 ° of the roughened nickel layer 12th more appropriately, the current density in accordance with the nickel ion concentration in the nickel plating bath (controlled by nickel sulfate hexahydrate (g / L) in the plating bath in the examples described later), the temperature of the nickel plating bath, the pH of the nickel plating bath, the ammonia concentration in the nickel plating bath, the To control halogen atom concentration in the nickel plating bath and the like.

The bath temperature of the nickel plating bath at the time of performing the plating of roughened nickel is not particularly limited, but is preferably 25 to 60 ° C, more preferably 25 to 50 ° C, and still more preferably 30 to 50 ° C, from the viewpoint that the lightness L. * and the gloss level of 85 ° of the surfaces of the roughened nickel layers 12th can be controlled more appropriately.

In the present embodiment, it is in performing plating of roughened nickel to precipitate the nickel grains 121 in an agglomerated state advantageous to carry out the nickel plating with stirring of the nickel plating bath. By stirring the nickel plating bath, the nickel grains become 121 in the agglomerated state slightly evenly on the metal base material 11 deposited, whereby the brightness L * and the gloss level of 85 ° of the surface of the roughened nickel layer 12th can be controlled more appropriately. The method of performing stirring is not particularly limited, and examples thereof include a method such as bubbling and pump circulation. As a condition for bubbling, there is no particular limitation on the kind of gas, but from the viewpoint of versatility, air is preferably used as the gas, and continuous ventilation for stable stirring is preferable as the timing for supplying a gas. As the amount of ventilation, since the desired roughened shape is hardly achieved if the stirring is too strong, the amount of ventilation is preferably 1 L / min or less with respect to the plating solution having a volume of 2 L. As a condition for the pump circulation, it is continuous Circulation preferable for stable stirring.

The amount of deposition at the time of nickel grain deposition 121 in an agglomerated state by plating roughened nickel is not particularly limited, but is preferably 0.89 to 4.45 g / m ² from the viewpoint of controlling the brightness L * and the degree of luster of 85 ° of the surfaces of the roughened nickel layer 12th to the above ranges, and from the viewpoint of further improving the adhesiveness of the nickel layer 12th on other components, the amount of deposition is at the time of deposition of the nickel grains 121 in an agglomerated state, more preferably 1.34 g / m ² or more, more preferably 1.60 g / m ² or more, and from the viewpoint of further improving the adhesiveness (plating adhesiveness) of the roughened nickel layer 12th to the metal base material 11 is the amount of precipitation at the time of precipitation of the nickel grains 121 in an agglomerated state, more preferably 4.01 g / m ² or less, still more preferably 3.56 g / m ² or less, and particularly preferably 3.12 g / m ² or less. Furthermore, from the viewpoint of emphasizing production efficiency and production cost, it is preferable that the ^{amount of precipitation be 1.34 to 2.23 g / m 2} when the nickel grains are used 121 be precipitated in the agglomerated state.

Then, in the manufacturing method of the present embodiment, the nickel grains become 121 precipitated by plating roughened nickel in an agglomerated state, and then the nickel grains become 121 with the nickel film 122 coated by further performing a covering nickel plating. Covering nickel plating for coating the nickel grains 121 with the nickel film 122 can be performed by any plating method of electrolytic plating or electroless plating, but it is preferably formed by electrolytic plating.

When the blanket nickel plating is carried out by the electrolytic plating method, for example, as the nickel plating bath, a Watts bath having a bath composition of 200 to 350 g / L nickel sulfate hexahydrate, 20 to 60 g / L nickel chloride hexahydrate and 10 to 50 g / L Boric acid can be used, and the nickel plating can be carried out under the conditions of pH 3.0 to 5.0, bath temperature of 40 to 70 ° C, current density of 5 to 30 A / dm ² (preferably 10 to 20 A / dm ² ) followed by washing with water.

The amount of deposition of the nickel film 122 (Coverage amount) for covering the nickel grains 121 with the nickel film 122 is not particularly limited. However, from the point of view that the lightness L * and the degree of gloss of 85 ° of the surfaces of the roughened nickel layers 12th can be appropriately controlled within the above ranges, the lightness is L * and the degree of gloss is 85 ° of the surfaces of the roughened nickel layers 12th can be appropriately controlled within the above ranges, it is preferably 4.45 to 26.70 g / m ² , and from the viewpoint of further improving the adhesiveness (plating adhesiveness) of the roughened nickel layer 12th is the amount of deposition of the nickel film 122 (Coverage amount) for covering the nickel grains 121 with the nickel film 122 preferably 6.23 g / m ² or more, and from the viewpoint of further improving the adhesiveness of the roughened nickel layer 12th on other components the amount of deposition of the nickel film is 122 (Coverage amount) for covering the nickel grains 121 with the nickel film 122 more preferably 19.58 g / m ² or less, and still more preferably 16.02 g / m ² or less. In addition, from the viewpoint of emphasizing production efficiency and production cost, the deposition amount of the nickel film is 122 to get the nickel grains 121 with the nickel film 122 to cover, more preferably 4.45 to 8.90 g / m ² . Further, the ratio between the amount of deposition by the plating of roughened nickel and the amount of deposition by the covering nickel plating is not particularly limited, but "the plating of roughened nickel: the deposition amount by the covering nickel plating" in weight ratio, is preferably 1: 2 to 1: 14, more preferably 2: 4.5 to 2:15, even more preferably 2: 5 to 2:15. It should be noted that in the case where the underlying nickel layer than the underlying metal plating layer 13th is formed when the covering nickel plating is performed, in addition to covering the nickel grains 121 with the nickel film 122 part of it contributes to the growth of the underlying nickel layer (thickening of a portion in which the underlying layer without the nickel grains is exposed). Therefore, in this case, the above-mentioned amount of deposition is the sum of the amount of coating by the nickel film 122 by the covering nickel plating and the amount of formation of the underlying nickel layer by the covering nickel plating.

Furthermore, in the present embodiment, it is from the viewpoint of further improving the adhesion between the metal base material 11 and the roughened nickel layer 12th preferred, an underlying metal plating layer 13th between the metal base material 11 and the roughened nickel layer 12th form, being the underlying metal plating layer 13th a nickel plating layer or a copper plating layer is preferred, with a nickel plating layer being more preferred. In particular, there are the nickel grains formed by the above-described plating of roughened nickel 121 in a state in which the particulate precipitates are aggregated and precipitated in the form of protrusions and exist as aggregates, and it is preferable to have gaps between the aggregates from the viewpoint of adhesion to other components, and therefore there are cases where the entire surface of the metal base material 11 is not completely covered. Therefore, it is, for example, in the case of using a steel sheet as a metal base material 11 in order to improve the effect of suppressing the occurrence of rust of the steel sheet, the underlying metal plating layer is advantageous 13th provide. Incidentally, in order to achieve such an effect of improving the corrosion resistance, it is preferable to use the metal base material 11 according to the application and perform an appropriate underlying plating process. When using sheet steel or copper as the metal base material 11 it is advantageous as the underlying metal plating layer 13th to form an underlying nickel plating layer or an underlying copper plating layer. Furthermore, when the nickel layer is applied by electrolytic nickel plating in the plating process of the underlying layer, it is possible to achieve good compatibility with the subsequent plating-plating process in order to achieve the plating adhesion of the roughened nickel layer 12th to improve further. Although the plating adhesion effect is only achieved by the blanket nickel plating process in a state where there is no underlying metal plating layer 13th since the blanket nickel plating process tends to prefer nickel on the nickel grains 121 From this point of view, it is preferable to precipitate the underlying metal plating layer 13th to form to improve corrosion resistance. When the metal base material 11 is a copper sheet, it is also possible to prevent the plating adhesion of the roughened nickel layer 12th to be further improved by carrying out an acid treatment or the like as a pretreatment.

The underlying metal plating layer 13th can be formed by the metal base material 11 is plated in advance before the roughened nickel layer 12th on the metal base material 11 is formed. In the case where the underlying metal plating layer 13th is the nickel plating layer, the nickel plating layer can be formed by any plating method such as electrolytic plating or electroless plating, preferably it is formed by electrolytic plating.

In the case where the underlying metal plating layer 13th the nickel plating layer is, if an electrolytic plating method is used as a method of forming the base nickel plating layer, for example, as the nickel plating bath, a Watts bath with a bath composition of 200 to 350 g / L nickel sulfate hexahydrate, 20 to 60 g / L nickel chloride can be used -Hexahydrate and 10 to 50 g / L boric acid can be used, and the nickel plating can be carried out under the conditions of pH 3.0 to 5.0, bath temperature from 40 to 70 ° C, current density from 5 to 30 A / dm ² (preferably 10 up to 20 A / dm ² ), followed by washing with water.

When the underlying metal plating layer 13th is formed, the deposition amount of the roughened nickel layer is 12th in the roughened nickel-plated sheet metal 1 of the present embodiment preferably 26.70 g / m ² or less, more preferably 4.45 to 22.25 g / m ² , even more preferably 4.45 to 17.80 g / m ² and particularly preferably 4.45 to 13.35 g / m ² from the viewpoint of further improving the adhesion between the metal base material 11 and the roughened nickel layer 12th .

When forming the underlying metal plating layer 13th is the total amount of deposition of the roughened nickel layer 12th and the underlying metal plating layer 13th in the roughened nickel-plated sheet metal 1 of the present embodiment is not particularly limited, but is preferably 5.0 to 50.00 g / m ² , more preferably 12.02 to 50.00 g / m ² , even more preferably 12.28 to 40.94 g / m ² and especially preferably 12.28 to 32.49 g / m ² from the viewpoint of improving the adhesion of the roughened nickel layer 12th on the metal base material 11 and the adhesion of the roughened nickel layer 12th on other components. In addition, from the viewpoint of emphasizing production efficiency and production cost, it is preferable that the total amount of deposition of the roughened nickel layer 12th and the underlying metal plating layer 13th Is 10.24 to 22.25 g / m ² . When high corrosion resistance is required, and especially when high adhesion of the roughened nickel layer 12th on the metal base material 11 and high adhesion of the roughened nickel layer 12th is required on other components, the total amount of deposition of the roughened nickel layer is 12th and the underlying metal plating layer 13th preferably 32.50 to 57.85 g / m ² . The total amount of deposition of the roughened nickel layer 12th and the underlying metal plating layer 13th can be determined by measuring the total amount of nickel on the roughened, nickel-plated sheet 1 can be determined using a fluorescence x-ray machine.

As described above, according to the present embodiment, as shown in FIG 3 shown the nickel grains 121 on the metal base material 11 precipitated in an agglomerated state by plating roughened nickel, and then, as in FIG 4th shown are the nickel grains 121 with the nickel film 122 coated by further covering nickel plating, and the brightness L * and the degree of gloss 85 ° of the surfaces of the roughened nickel layer 12th can be controlled in the above areas.

In particular, when performing the plating of roughened nickel or when performing the covering nickel plating further after the plating of roughened nickel, as in FIG 3 shown, an aggregate of protrusions (pillars) is formed, consisting of secondary particles (nickel grains 121 ) exist in which primary particles are aggregated. On this point, the inventors of the present invention made studies and as a result obtained the following knowledge.

That is, in the above case, by adjusting the plating conditions, it is possible to control the size, shape and density of the above aggregate, whereby it has been found that it is possible to both have good plating adhesion to the metal base material 11 as well as to achieve good adhesion to other components in a suitable manner. In addition, it was found that despite Rz _jis as a parameter that represents the difference in height in the surface, the adhesion to other components and the adhesion of the roughened nickel layer 12th cannot be controlled simply by setting Rz _jis or other parameters that represent roughness, such as Ra and Rz. This means that although there is a tendency to ensure adhesion to other components through a certain height difference (Rz _jis ), if the height difference (Rz _jis ) is too great, the roughened nickel layer tends to adhere 12th to the metal base material 11 to deteriorate. In particular, however, it was found that the adhesion of the roughened nickel layer 12th on the metal base material 11 not only determined by Rz _jis alone becomes. In addition, it was found that the density of the above aggregate in the roughened nickel layer 12th is too high to allow resin or the like to penetrate between the above aggregate and to ensure adhesiveness to other members such as a resin film or the like. On the other hand, it has been found that if the density of the above aggregate is too low, the individual above aggregates may be finely broken and the adhesiveness of the roughened nickel layer may be broken 12th on the metal base material 11 is likely to be reduced, or the foregoing aggregates themselves are too small to obtain the anchoring effect and the adhesiveness to other members such as the resin film is not obtained. On the other hand, it has heretofore been difficult to measure the size, shape and density of such a protruding aggregate and specify an appropriate range therefor.

Under the circumstances, the inventors of the present invention further studied that as parameters for substituting such sizes, shapes and densities, referring to the two parameters of the brightness L * and the gloss level of 85 ° of the roughened nickel layer 12th have concentrated, both the brightness L * and the gloss level of 85 ° are in the specified ranges if the adhesion of the roughened nickel layer 12th to the base material and the adhesion to other components is good.

In particular, although it is well known that the numerical value of the lightness L * fluctuates depending on the unevenness of the sheet surface, the inventors of the present invention found that in that of the secondary particles (nickel grain material 121 ) formed above aggregate, as in 3 shown, not only the size (Rz _jis ) of the protrusion but also the size of the primary particles of the plated particles at the tip of the protrusion have a great influence. That is, it is found that the brightness L * varies by changing the surface shape of the tip of the above aggregate due to the size of the particle size of the primary particles.

Furthermore, the inventors of the present invention found the problem that the adhesion of the roughened nickel layer 12th on the metal base material 11 can be worse even if the brightness L * is in a suitable range. In particular, in such cases, it is assumed that the plating particles on the surfaces of the above aggregates are large and relatively smooth so that the brightness L * is in an appropriate range, while the plating particles are large and porous so that the plating particles easily separate from the metal base material 11 to solve. One of the reasons for this is considered to be that, in the case of large clad particles, the above aggregates tend to break and fall off because Rz _jis tends to be high. The measurement of the plated particles is therefore very time-consuming; in the case that such plated particles are large, it has been found that the degree of gloss measured at a low angle of incidence of light with respect to the plated sheet and the degree of gloss of 85 ° together are extremely low.

Based on these findings, the inventors of the present invention have a roughened nickel-plated sheet 1 designed in which the brightness L * and the gloss level of 85 ° of the roughened nickel layers 12th lie within the above specified ranges.

As described above, in the present embodiment, as a roughened nickel layer 12th Aggregates having a protruding shape (columnar) are provided on the surface so that adhesion to other components such as a resin film can be ensured. Then, the inventors of the present invention investigated that the plating layer having such above aggregates can be formed by performing the plating under the situation of current conduction under the condition that the supply of nickel ions is insufficient with respect to the plating current. That is, it may be formed by insufficient supply of nickel ions with respect to the plating current to cause abnormal electrodeposition.

On the other hand, in such abnormal electrodeposition, since the abnormal electrodeposition mode changes depending on the nickel concentration in the plating solution, the bath temperature of the plating solution, the pH of the plating solution, the current density at the time of plating, and the like, it is difficult to obtain a roughened, nickel-plated sheet metal that has both the adhesiveness of the roughened nickel layer 12th on the metal base material 11 as well as the adhesion of the roughened nickel layer 12th on other components at the same time by simply performing plating under the condition that causes abnormal electrodeposition. In particular, according to the abnormal electrodeposition method, since the asperities are easily formed while easy adhesion to other components can be achieved and easily deposited plating particles fall off, there is a case that they fall off during handling. On the other hand, the inventors of the present invention have found that to solve the problem, at the same time both the adhesiveness of the roughened nickel layer 12th on the metal base material 11 as well as the adhesion of the roughened nickel layer 12th on other components to meet the size of the primary particles, the size of the protruding aggregate and the shape of the protruding aggregate containing the roughened nickel layer 12th educates are important.

Here is 7 (B) a diagram showing a specific mode of the roughened nickel layer 12th according to the present embodiment, and FIG. 13 is a schematic diagram based on a FIG 5 (D) and 14 (A) SEM image of the roughened nickel layer shown 12th based. Furthermore is 7 (A) FIG. 13 is a diagram showing one aspect of the plating layer obtained by plating roughened nickel, and FIG 14 (B) SEM image shown. In the 7 (B) The embodiment shown in FIG 7 (A) The embodiment shown is obtained by plating roughened nickel and then applying covering nickel plating to the plating layer. By the way, is in 7 (A) and 7 (B) the case in which the underlying nickel plating layer is formed is exemplified, but it is not particularly limited to the embodiment in which the underlying nickel plating layer is formed (the same applies to 8 (A) to 8 (C) , 9 (A) to 9 (D) and 10 (A) to 10 (D) ).

That is, according to the inventors of the present invention, like the roughened nickel layer 12th , has been modified by the embodiment as in 7 (B) shown, in particular by fulfilling the following conditions ( 1 ) to (4), found that the above problems can be solved. That is, (1) the primary particles constituting the above aggregate are not too small and have an appropriate size (the mean particle diameter of the primary particles is preferably 0.3 to 3.0 µm, more preferably 0.5 to 2.0 µm ), (2) the shape of the aggregate of the secondary particles on which such primary particles are aggregated is protruding or columnar, (3) the height of the aggregate is not too low and not too high (the height is preferably 1 to 20 µm, more preferably 2 to 15 µm, from the viewpoint of emphasizing production efficiency and production cost, particularly preferably 2.0 to 10.0 µm), and (4) the inventory density of the aggregate is not too small (the aggregates are not too close to each other (the The distance is not too small and the units are not too close together)). If the primary particles are too small, the adhesion (bonding) between the primary particles becomes poor and the adhesion of the plating decreases. If the primary particles are too large, it becomes impossible to adopt a protrusion or a columnar type, or local protrusions will excessively grow, the protrusions are likely to break due to an external force or the like, and as a result, the plating adhesion becomes a poor condition.

Here the term means “not too small and of a reasonable size”, more precisely, as indicated by the in 5 (C) and 5 (D) SEM cross-sectional images shown of the roughened nickel layer 12th confirmed a state in which 70% or more of the total of the primary particles constituting the protruding or columnar secondary particles are primary particles having a particle diameter of 0.3 to 3.0 µm, more preferably primary particles having a particle diameter of 0.5 up to 2.0 µm. Incidentally, 70% or more of the above-described whole means that 70% or more of the cross-sectional area of the total primary particles is the area derived from the particles with the above-mentioned particle size range. In addition, although it is difficult to deduce the particle diameter of each particle from the SEM cross-sectional photograph, if the particle diameter of the primary particles constituting the secondary particles is too small, the proportion of the particles with a particle diameter of less than 0.3 µm becomes apparent 70% or more so that it can be clearly identified.

Furthermore, according to the in 7 (B) It was found that the lightness L * and the degree of gloss of 85 ° fall within the predetermined range of the present invention, and both the adhesiveness of the roughened nickel layer 12th on the metal base 11 as well as the adhesion to other components are fulfilled at the same time.

On the other hand, the in 7 (A) shown embodiment, in which the covering nickel plating is not performed because the primary particles are very fine or the height of the above aggregate is small, the brightness L * outside the predetermined range of the present invention, and the adhesiveness of the roughened nickel layer 12th on the metal base material 11 or the adhesion to other components is poor. It should be noted that the in 7 (A) The embodiment shown is an embodiment similar to the comparative examples described later 11 corresponds to 16 and 34.

In addition, the in 8 (A) embodiment shown in the in 8 (B) embodiment shown, which is obtained by applying a covering nickel plating, and in which in FIG 8 C) shown embodiment, in which the roughened nickel layer is not formed, the height of the protruding aggregate is small or the protruding aggregate itself is not formed, the lightness L * is outside the predetermined range of the present invention, and the adhesiveness of the roughened nickel layer 12th on the metal base material 11 or the adhesion to other components is poor. In the 8 (A) The embodiment shown is the embodiment corresponding to Comparative Examples 17 to 20 described later and shown in FIG 8 (B) and 8 (C) Embodiments shown are embodiments similar to the comparative examples described later 1 to 4, 33, 37 to 39 correspond.

Furthermore, in the in 9 (A) embodiment shown and in the in 9 (B) shown embodiment, which is obtained by applying a covering nickel plating, since the influence of the unevenness of the surface of the underlying nickel plating layer or the influence of the coarsening of the secondary particles contained in the roughened nickel layer is great, is in the 9 (A) shown embodiment, the gloss level of 85 ° is outside the predetermined range of the present invention and the adhesion of the roughened nickel layer 12th on the metal base material 11 impaired. Furthermore, the in 9 (B) As shown in the embodiment shown, the brightness L * is outside the predetermined range of the present invention, and it becomes inferior in adhesion to the other components. In the 9 (A) The embodiment shown is the embodiment corresponding to Comparative Example 24 described later and shown in FIG 9 (B) The embodiment shown is the embodiment corresponding to Comparative Example 10 described later.

In addition, the in 9 (C) embodiment shown and in the in 9 (D) shown embodiment obtained by applying blanket nickel plating is formed as an aggregate with voids or a porous aggregate, and the gloss level of 85 ° is outside the predetermined range of the present invention, and the adhesion of the roughened nickel layer 12th on the metal base material 11 is worse. In the 9 (C) The embodiment shown is the embodiment corresponding to Comparative Examples 30, 31 described later; in the 9 (D) The embodiment shown is the embodiment corresponding to Comparative Examples 8, 9 described later.

Furthermore, the in 10 (A) embodiment shown and in the in 10 (B) shown embodiment obtained by applying blanket nickel plating thereto because the height of the above aggregate is too high and the formation density of the above aggregate is low, the brightness L * outside the predetermined range of the present invention, and the adhesion of the roughened nickel layer 12th on the metal base material 11 is worse. In the 10 (A) The embodiment shown is the embodiment corresponding to Comparative Examples 21 to 23, 25 to 29, 35, 36 described later; in the 10 (B) The embodiment shown is the embodiment corresponding to Comparative Example 5 described later.

Furthermore, in the in 10 (C) embodiment shown and in the in 10 (D) shown embodiment obtained by applying blanket nickel plating, the height of the above aggregate is too high, and the lightness L * and the gloss level of 85 ° are outside the predetermined range of the present invention, and the adhesion of the roughened nickel layer 12th on the metal base material 11 is worse. In the 10 (C) The embodiment shown is the embodiment corresponding to Comparative Example 32 described later; in the 10 (D) The embodiment shown is the embodiment corresponding to Comparative Examples 6, 7 described later.

Then, the inventors of the present invention found that in the above embodiments in 7 (A) , 8 (A) to 8 (C) , 9 (A) to 9 (D) and 10 (A) to 10 (D) the lightness L * and the gloss level of 85 ° are each outside the predetermined range of the present invention, and the adhesion of the roughened nickel layer 12th on the metal base material 11 and the adhesion to other components deteriorates. In contrast, in the case of the in 7 (B) As shown in the embodiment shown, it was found that the lightness L * and the gloss level of 85 ° are within the predetermined range of the present invention, and both the adhesion of the roughened nickel layer 12th on the metal base material 11 as well as the adhesion to other components can be fulfilled at the same time.

The process of forming the roughened nickel layer 12th , as in 7 (B) shown includes the method described above, and in this case, for example, it is concluded that the roughened nickel layer 12th , as in 7 (B) is formed by a precipitation step and a growth step described below. That is, first, as described above, as the roughened nickel layer, by passing a suitable current into the dilute nickel aqueous solution (application of a voltage) to stimulate precipitation, it is possible to remove the metallic nickel at once from a number of To precipitate germs, and it is possible to suppress the growth in the plane direction of the precipitated particles to some extent. At this time, since the nuclei of the primary particles tend to preferentially precipitate on the convex portions formed by the precipitated particles, the primary particles of the plated grains are stacked in the height direction, and the shape of the secondary particles in which the primary particles are aggregated, can be made into a head start. However, even if such an aggregate is formed, if the primary particles are too small, the contact area between the primary particles is too small, as in 7 (A) shown so that the primary particles can peel off. Therefore, as described above, after the roughened nickel is plated, the covering nickel plating is carried out. Although the term “covering” is used here, research by the inventors of the present invention has confirmed that after such covering nickel plating, in addition to the precipitation covering the primary particles formed by the plating of roughened nickel, grain growth actually occurs in which the primary particles grow. In particular, it is assumed that the growth of such primary particles by covering nickel plating takes place not only on the upper surface of the above aggregate, but also on the particles on the side surface of the aggregate and the particles inside the aggregate. As a result, the primary particles are considered to have an appropriate size, thereby improving the adhesion between the primary particles and also increasing the thickness of the above aggregate and making it difficult to break. Therefore the nickel layer has been roughened 12th that the in 7 (B) The embodiment shown is good adhesion of the roughened nickel layer 12th on the metal base material 11 . Because the roughened nickel layer 12th in addition, has a protruding aggregate that is of reasonable height, it also adheres well to other components.

In the present embodiment, as a method of forming the roughened nickel layer as shown in FIG 7 (B) has shown a method of applying blanket nickel plating after the plating of roughened nickel when the conditions described above ( 1 ) to (4) are satisfied after the roughened nickel plating, of course, if the lightness L * and the gloss level of 85 ° are within the predetermined range of the present invention, the roughened nickel-plated sheet excellent in the adhesion of the roughened nickel layer can be obtained 12th on the metal base material 11 and the adhesion to the other component. Therefore, the nickel-plating step can be omitted.

It should be noted that a cross-sectional SEM image of the roughened nickel layer according to the in 8 (A) embodiment shown in 11 (A) is shown. A cross-sectional SEM image of the roughened nickel layer according to the in 8 (B) embodiment shown is in 11 (B) shown. A cross-sectional SEM image of the roughened nickel layer according to the in 8 (C) embodiment shown is in 11 (C) shown. A cross-sectional SEM image of the roughened nickel layer according to the in 9 (A) embodiment shown is in 12 (A) shown. A cross-sectional SEM image of the roughened nickel layer according to the in 9 (B) embodiment shown is in 12 (B) shown. A cross-sectional SEM image of the roughened nickel layer according to the in 9 (C) embodiment shown is in 12 (C) shown. A cross-sectional SEM image of the roughened nickel layer according to the in 10 (A) embodiment shown is in 13 (A) shown. A cross-sectional SEM image of the roughened nickel layer according to the in 10 (C) embodiment shown is in 13 (B) shown.

According to the roughened nickel-plated sheet 1 of the present embodiment, as described above, since the adhesion of the roughened nickel layer 12th on the metal base material 11 good and the adhesion to other components is excellent, it can be used for applications used by bonding with other components such as various containers where the adhesion is to different components such as resin and active material, a component of an electronic Device (such as a substrate), a component of the battery (outer housing, current collector, connection cable).

In particular, the roughened nickel-plated sheet 1 of the present embodiment because of the adhesion of the roughened nickel layer 12th , ie the adhesion to the base material 11 , is excellent, for example, even if the coated sheets overlap or touch, the roughened nickel layer 12th in the surface can only be peeled off or fall off with difficulty, in a suitable manner as a roughened nickel-plated sheet metal 1 with a roughened nickel layer 12th on the outermost surface of both surfaces, as in 1A shown to be used.

On the other hand, if the adhesion to the other component is only required on one side of the clad sheet, it is sufficient that the roughened nickel layer 12th is formed only on one side, as with the one in 1B shown roughened nickel-plated sheet metal 1 . On the surface without the formation of the roughened nickel layer 12th can, although the metal base material 11 Located on the outermost surface when the metal base material 11 a steel sheet is this an untreated steel sheet, or it remains can be subjected to surface treatment such as nickel plating, electroplating and chemical conversion treatment according to the required properties. In particular, when resistance to an alkaline solution is required, a roughened nickel-plated steel sheet in which a normal nickel-plating layer (e.g., a nickel-plating layer formed under the above-mentioned conditions to form an underlying nickel-plating layer) is formed on the surface the roughened nickel layer 12th is not formed by forming the normal nickel plating layer on both surfaces of the metal base material 11 covered with a nickel layer, which is preferred.

During the production of the roughened, nickel-plated sheet metal 1 , as in 1B As shown, in the step of performing the plating of roughened nickel, the roughened nickel-plated sheet having a roughened nickel layer 12th only on one side, for example by a method of performing the plating without electrification on the surface of the side that does not have the roughened nickel layer 12th or obtained by a method of performing masking.

EXAMPLES

The present invention is described in more detail below with reference to examples, although the present invention is not limited to these examples.

Here, the evaluation method for each characteristic is as follows.

<Surface roughness>

On the surface of the roughened nickel-plated sheet on which the roughened nickel layers were formed, a field of view of 97 μm × 129 μm (length × width) (measuring field width of 129 μm, measuring range of about 12,500 μm ² (12,500 ± 100)) with a Laser microscope (manufactured by Olympus Co, Ltd., model number: OLS3500) is scanned in accordance with JIS B0601: 2013, and then the field of view is analyzed with an analysis software (software name: LEXT-OLS) under the condition of the analysis mode: roughness analysis, where the arithmetic mean value of the roughness Ra and the ten-point mean roughness Rz _{jis were} measured. It should be noted that the cut-off value at the time of measurement by a laser microscope was a wavelength of about 43 µm (43.2 on the display), which corresponds to a length of 1/3 of the measuring field width (129 µm).

<Nickel content>

In the present example, the amount of nickel in the underlying nickel layer and the roughened nickel layer (nickel grains and nickel film) was determined by measurement with a fluorescent X-ray device after the respective steps of forming the underlying nickel layer, the nickel grains and the nickel film. Specifically, the amount of nickel in the underlying nickel layer was determined once by using a fluorescent X-ray apparatus at the time the underlying nickel layer was formed. Thereafter, after the nickel grains were formed, the total amount of nickel was determined again with a fluorescent X-ray apparatus, and the difference between the total amount of nickel obtained and the amount of nickel in the underlying nickel layer was defined as the amount of nickel in the nickel grains . Further, after the formation of the nickel film, the total amount of nickel was determined again with a fluorescent X-ray apparatus, and the difference between the total amount of nickel before the formation of the nickel film and the total amount of nickel after the formation of the nickel film was determined, whereby the amount of nickel in the nickel film was determined was determined in the same way. Then, the amount of nickel in the entirety of the nickel grains and the nickel film was determined as the amount of deposition of the roughened nickel layer.

In this case, where a nickel-containing metal such as a stainless steel sheet or a nickel sheet is used as the base material, the amount of nickel in each layer cannot be measured by the above-mentioned fluorescent X-ray machine. Therefore, using a base material not containing nickel such as a steel sheet, initially under a plating condition in which an underlying nickel layer having the predetermined amount of nickel is obtained, a metal sheet containing nickel such as a stainless steel sheet becomes and a nickel sheet, is electrolyzed so that it is possible to make it one with the same amount of deposition.

Note that, although the measurement of the amount of nickel in the present examples and the comparative examples is performed by the above method, the measurement method of the amount of nickel is not limited to such a method, and the following method can be used. In the present example, the following procedures have also been partially adopted. That is, first of all, the roughened nickel-plated sheet in which the underlying nickel layer, the nickel grains and the nickel film are formed is measured with a fluorescent X-ray machine to determine the total amount of nickel in the layers formed in the roughened, nickel-plated sheet . Then, by cutting the roughened, nickel-plated sheet and observing the cross-section with a scanning electron microscope (SEM) to measure the thickness of the underlying nickel layer, the amount of nickel derived from the thickness of the underlying nickel layer is determined, which is the Amount of nickel in the underlying nickel layer. Then, by subtracting the amount of nickel of the underlying nickel layer from the total amount of nickel, the total amount of nickel of the nickel grains and the nickel film is obtained, and this can be used as the deposition amount of the roughened nickel layer. In particular, when the blanket nickel plating is performed, the nickel film forms 122 in addition to the fact that the nickel film 122 the roughened nickel layer 12th by covering the nickel grains 121 forms the underlying nickel layer in part of it. Therefore, according to such a method, the amount of nickel of the underlying nickel layer can be obtained in consideration of the growth (thickening) of the underlying nickel layer by the covering nickel plating.

When observing the cross section with a scanning electron microscope (SEM), the boundary between the metal base material and the underlying nickel layer and the boundary between the underlying nickel layer and the roughened nickel layer, as shown in FIG 15th shown, determined. That is, for the boundary between the metal base material and the underlying nickel layer, as in FIG 15th shown, the boundary between the metal base material and the underlying nickel layer was identified as that in 15th position shown (dashed position below), since, as in 15th shown can be clearly observed. For the boundary between the underlying nickel layer and the roughened nickel layer, as in 15th shown, the boundary between the underlying nickel layer and the roughened nickel layer under the roots of the protrusion formed from the secondary particles was determined to be the lowest position (dashed line position above). By the way is 15th a diagram for explaining the determination method of the boundary between the metal base material and the underlying nickel layer and the boundary between the underlying nickel layer and the roughened nickel layer in the examples and comparative examples. 15 (A) and 15 (B) show side by side the same scanning electron microscope (SEM) image; in 15th are the respective limit positions in 15 (B) indicated by a dashed line.

<Brightness L *>

The lightness L * of the surface of the roughened nickel layer was measured with a spectrophotometer (product name “CM-5”, manufactured by Konica Minolta, Inc.) according to the geometric condition C in JIS Z8722 by the SCE method (method of removing specular reflected light , "Specular reflected light removing method").

<85 ° gloss level>

The gloss level of 85 ° of the surface of the roughened nickel layer was measured with a gloss meter (product name “VG 7000”, manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS Z8741. When the gloss level of 60 ° was measured with the same measuring device, it was less than 1.5 in all examples (examples 1 to 32).

<Adhesion of the roughened nickel layer>

First, as a reference sample, an adhesive tape (product name "Cellotape (Registered Trade Mark)", manufactured by Nichiban Co., Ltd.) adhered to the backing paper was prepared, and the lightness L * and the color value a *, b * were determined with was measured by a spectrophotometer (product name "CM-5", manufactured by Konica Minolta, Inc.). The CIE1976L * a * b * color difference models were used for the measurement.

• 5 Punkte: ΔE*ab ist kleiner als 1
• 4 Punkte: ΔE*ab ist 1 oder mehr und weniger als 10
• 3 Punkte: ΔE*ab ist 10 oder mehr und weniger als 30
• 2 Punkte: ΔE*ab ist 30 oder mehr und weniger als 40
• 1 Punkt: ΔE*ab ist 40 oder mehr

Then, an adhesive tape (product name "Cellotape (Registered Trade Mark)", manufactured by Nichiban Co., Ltd.) was attached to the surface of the roughened nickel-plated sheet obtained in Examples and Comparative Examples on which the roughened nickel layer was formed, so as to be a width of 24 mm and a length of 50 mm, and then a peeling test was carried out using the attached adhesive tape according to the peeling test method described in JIS H8504. Then, after the peeling test, the adhesive tape was stuck on the same backing paper as the above reference sample, and the lightness L * and the color value a *, b * were measured with a spectrophotometer in the same manner as described above. These differences ΔE * ab (ΔE * ab = [(ΔL *) ² + (Δa *) ² + (Δb *) ² ] ^1/2 ) and evaluated the adhesion of the roughened nickel layer on the basis of the following criteria. It should be noted that the smaller ΔE * ab, the lower the amount of peeling in the peeling test, i.e. the higher the residual rate of the roughened nickel layer after the peeling test and the better the adhesion of the roughened nickel layer to the metal base material can be assessed.

• 5 points: ΔE * ab is less than 1
• 4 points: ΔE * ab is 1 or more and less than 10
• 3 points: ΔE * ab is 10 or more and less than 30
• 2 points: ΔE * ab is 30 or more and less than 40
• 1 point: ΔE * ab is 40 or more

<Adhesion (T-peel strength) of polypropylene resin (PP resin)>

The roughened, nickel-plated sheets obtained in the examples and comparative examples were cut into two test master sheets each having a width of 15 mm and a length of 50 mm, which were used as T-peel test pieces. Then the two T-peel test pieces were each bent so that the bending angle at a position of length 20 mm is 90 °. Then, the surfaces with a roughened nickel layer were opposed to each T-peel test piece, and a polypropylene resin sheet having a width of 15 mm, a length of 15 mm and a thickness of 60 µm (product name “Modic”, polypropylene resin two-layer sheet manufactured by Mitsubishi Chemical Corporation, an adhesive surface used for evaluation is an adhesive surface between a polypropylene resin and a T-peel test piece, and the product name "Modic" is an adhesive layer for stabilizing a test) was put therebetween, and heat sealing was carried out among the following Conditions conducted: temperature: 190 ° C, pressing time: 5 seconds, and heat sealing pressure: 2.0 kgf / cm ² , and two T-peel test pieces were bonded via a polypropylene resin sheet. The position where the polypropylene resin sheet is sandwiched is a longitudinal end portion of a T-peel test piece, and the whole of the polypropylene resin sheet becomes an adhesive surface. The T-peel test piece thus prepared is subjected to a tensile test with a tensile tester (universal material tester Tensilon RTC-1350A, manufactured by ORIENTEC CORPORATION), and the peel load (T peel strength) is measured. The measurement conditions were a pulling speed of 10 mm / min at room temperature. It can be judged that the higher the T-peel strength, the better the adhesion to the resin.

<< Example 1 »

A steel sheet is used as the substrate, which is produced by annealing a cold-rolled sheet of aluminum killed steel with a low carbon content (thickness 0.25 mm).

Then, the produced steel sheet was subjected to alkaline electrolytic degreasing and pickling by immersion in sulfuric acid, followed by electrolytic plating under the following conditions using an underlying nickel plating bath having the following bath composition to form underlying nickel layers on both surfaces of the steel sheet to build.

<Conditions for the underlying nickel plating>

• Bath composition: 250 g / L nickel sulfate hexahydrate, 45 g / L nickel chloride hexahydrate and 30 g / L boric acid
• pH value: 4.2
• Bath temperature: 60 ° C
• Current density: 10 A / dm ²
• Plating time: 30 seconds

Next, the steel sheet on which the underlying nickel layer was formed was subjected to electrolytic plating (plating of roughened nickel) under the following conditions using a plating bath for roughened nickel having the following bath composition, with the nickel grains on the underlying nickel layer both sides of the steel sheet were precipitated.

<Conditions for plating roughened nickel>

• Bath composition: 20 g / L nickel sulfate hexahydrate and 20 g / L ammonium sulfate
• pH value: 6.2
• Bath temperature: 30 ° C
• Current density: 20 A / dm ²
• Plating time: 11 seconds

Next, the steel sheet, on which nickel grains were precipitated on the underlying nickel layer, was subjected to electrolytic plating (covering nickel plating) under the following conditions by using a bath for covering nickel plating with the following bath composition to form the layers on the underlying nickel layer to cover precipitated nickel grains with a nickel film, thereby obtaining a roughened nickel-plated sheet of Example 1.

<Conditions for covering nickel plating>

• Bath composition: 250 g / L nickel sulfate hexahydrate, 45 g / L nickel chloride hexahydrate and 30 g / L boric acid
• pH value: 4.2
• Bath temperature: 60 ° C
• Current density: 10 A / dm ²
• Plating time: 30 seconds

The roughened nickel-plated sheet obtained was subjected to measurements and evaluations of the amounts of nickel in the underlying nickel layer, the nickel grains and the nickel film, the brightness L * and the gloss level of 85 ° of the surfaces of the roughened nickel layer, the adhesion of the roughened nickel layer and the adhesion of the polypropylene resin (PP resin). The results are shown in Table 1.

<< Examples 2 to 15 »

The roughened nickel-plated sheets of Examples 2 to 15 were obtained and evaluated in the same manner as in Example 1, except that the plating bath and plating conditions of the plating of roughened nickel were changed to the conditions shown in Table 1, and the processing time of the covering Nickel plating was changed so that the deposition amount of the nickel film to be formed became the amount shown in Table 1. The results are shown in Table 1.

<< Examples 16 to 31 »

The roughened nickel-plated sheets of Examples 16 to 31 were obtained and evaluated in the same manner as in Example 1, except that the plating conditions of the plating of roughened nickel were changed to the conditions shown in Table 2 and the processing time of the covering nickel plating was so changed that the deposition amount of the nickel film to be formed became the amount shown in Table 2. The results are shown in Table 2.

«Example 32»

The roughened nickel-plated sheet of Example 32 was obtained and evaluated in the same manner as in Example 1 except that a copper sheet (electrolytic copper foil manufactured by Fukuda Metal Foil & Powder Co., Ltd. (Ra: 0.1 µm, Rz _jis : 1.7 µm as values measured by laser microscopy)) was used as the metal base material, the plating conditions of roughened nickel were changed to the conditions shown in Table 2, and the processing time of the covering nickel plating was changed so that the deposition amount of the to be formed Nickel film became the amount shown in Table 2. The results are shown in Table 2.

<< Examples 33 to 36 >>

The roughened nickel-plated sheets of Examples 33 to 36 were obtained and evaluated in the same manner as in Example 1, except that the conditions for plating roughened nickel were changed to the conditions shown in Table 2 and the processing time of the covering nickel plating was changed became that the deposition amount of the nickel film to be formed became the amount shown in Table 2. The results are shown in Table 2.

«Examples 37 to 41»

The roughened nickel-plated sheets of Examples 37 to 41 were obtained and evaluated in the same manner as in Example 1, except that SUS304 (Example 37), SUS316 (Example 38), SUS430 (Example 39), SUS444 (Example 40) and pure Nickel sheet (Example 41) were used as metal base materials, and the conditions for plating roughened nickel were changed to the conditions shown in Table 2, and the processing time for blanket nickel plating was changed so that the deposition amount of the nickel film to be formed was as shown in Table 2 set was shown. The results are shown in Table 2. Note that, in Examples 37 to 41, SUS304, SUS316, SUS430, SUS444 and pure nickel sheet were used, and after pickling in sulfuric acid immersion, the underlying nickel layers were after electrolysis (impact nickel plating) under the following conditions by using a Nickel plating baths formed with the following bath compositions.

<Conditions for blown nickel plating>

• Bath composition: 250 g / L nickel sulfate hexahydrate, 50 g / L sulfuric acid 50g / L
• pH value: 1.0 or less
• Bath temperature: 60 ° C
• Current density: 30 A / dm ²
• Plating time: 5 seconds

<< Comparative examples 1 until 10"

The roughened, nickel-plated sheets of the comparative examples 1 to 10 were obtained and evaluated in the same manner as in Example 1, except that the conditions for plating roughened nickel and covering nickel plating were changed to the conditions shown in Table 3. The results are shown in Table 3.

«Comparative Examples 11 to 22»

The roughened, nickel-plated sheets of the comparative examples 11 through 22 were obtained and evaluated in the same manner as in Example 1, except that the conditions for plating roughened nickel were changed to the conditions shown in Table 3 and blanking nickel plating was not performed. The results are shown in Table 3.

<< Comparative Examples 23, 24 >>

The roughened nickel-plated sheets of Comparative Examples 23 and 24 were produced and evaluated in the same manner as in Example 1, except that a copper sheet was used as the metal base material was changed, the conditions for plating roughened nickel were changed to the conditions shown in Table 4 and blanking nickel plating was not performed. The results are shown in Table 4. In Comparative Example 23, an electrolytic copper foil manufactured by Fukuda Metal Foil & Powder Co., Ltd. was used. (Ra: 0.1 µm, Rz _jis : 1.7 µm in terms of values measured by laser microscopy) as the copper sheet, and in Comparative Example 24, a copper foil whose surfaces were roughened by performing plating of roughened copper on the same copper foil as in Comparative Example 23 was used were used as copper sheet.

«Comparative Examples 25 to 32»

The roughened nickel-plated sheets of Comparative Examples 25 to 32 were obtained and evaluated in the same manner as in Example 1, except that the conditions for plating roughened nickel were changed to the conditions shown in Table 4 and blanking nickel plating was not performed. The results are shown in Table 4.

«Comparative Example 33»

The roughened, nickel-plated sheets of Comparative Example 33 were produced and evaluated in the same manner as in Example 1, with the difference that neither a roughened nickel plating nor a covering nickel-plating was carried out. The results are shown in Table 4.

«Comparative Examples 34 to 36»

The roughened nickel-plated sheets of Comparative Examples 34 to 36 were obtained and evaluated in the same manner as in Example 1, except that the conditions for plating roughened nickel were changed to those shown in Table 4 and the covering nickel plating was not was carried out. The results are shown in Table 4.

«Comparative Examples 37 to 39»

The roughened nickel-plated sheets of Comparative Examples 37 to 39 were obtained and evaluated in the same manner as in Example 1, except that the conditions for the plating of the roughened nickel and the covering nickel plating were changed to the conditions shown in Table 4. The results are shown in Table 4.

As can be confirmed from Tables 1 to 4, when the lightness L * of the surface of the roughened nickel layer was 30 to 50 and the degree of luster was 85 ° of the surface of the roughened nickel layer 1.5 to 50, the adhesion of the roughened nickel layer to the metal base material was good, and the adhesion to the polypropylene resin (PP resin) was excellent (Examples 1 to 36).

On the other hand, when the roughened nickel layer was not formed or when the lightness L * or the gloss level of 85 ° of the surface of the roughened nickel layer was outside the specified ranges defined in the present invention, the adhesion of the roughened nickel layer to the metal base material was and / or the adhesion to the polypropylene resin (PP resin) is worse (comparative examples 1 to 39).

By the way are 5 (A) and 5 (B) Photographs obtained by observing the surface of the roughened, nickel-plated sheet of Example 28 with a scanning electron microscope (SEM), 5 (C) and 5 (D) are photographs obtained by observing the cross section of the roughened nickel-plated sheet of Example 28 with a scanning electron microscope (SEM). Furthermore are 6 (A) and 6 (B) Photographs obtained by observing the surface of the roughened nickel-plated sheet of Comparative Example 5 with a scanning electron microscope (SEM), 6 (C) and 6 (D) are photographs obtained by observing the cross section of the roughened nickel-plated sheet of Comparative Example 5 with a scanning electron microscope (SEM).

It should be noted that in 5 (A) to 5 (D) , 6 (A) to 6 (D) the scale bars (white lines) in the section describing the measurement conditions at the bottom left of the figure each indicate a length of 1 µm.

Furthermore, in Table 1 to Table 4, the amount of nickel deposited on the underlying nickel layer was calculated from the processing conditions for the underlying nickel plating, and the calculated amount was referred to as the “underlying nickel layer”. Also the amount of deposition of the nickel plating of the nickel film 122 was calculated from the processing conditions in the covering nickel plating, and the calculated amount was described as "nickel film". It should be noted that when performing the covering nickel plating, the nickel film is the roughened nickel layer 12th as a nickel film 122 which forms the nickel grains 121 covers, and also a part of it forms the underlying nickel layer. That is, it also contributes to the growth of the underlying nickel layer. In fact, the thickness of the formed underlying nickel layer was calculated by scanning electron microscopy (SEM), and the amount of nickel of the underlying nickel layer was calculated from the calculated thickness, and it was 11.6 g / m ² in Example 5, 11, 6 g / m ² in Example 6, 12.5 g / m ² in Example 7, and 13.4 g / m ² in Example 8. By calculating the difference between these values and the calculated values from the plating processing conditions of Examples 5 to 8, it is possible to calculate the growth of the underlying nickel layer. Similarly, in Examples 1 to 36, a difference of 1.8 to 4.5 g / m ^{2 was} calculated (shown in Table 1 and Table 2). In addition, the mean values were also 2.8 g / m ² . Note that in Table 1 and Table 2, the nickel thickness (µm) of the underlying nickel layer, measured from the scanning electron microscope (SEM) cross-sectional photograph, is shown in the third column from the right, and the amount of nickel (g / m ² ) the underlying nickel layer, calculated from the nickel thickness of the underlying nickel layer, is shown in the second column from the right. In addition, the rightmost columns in Table 1 and Table 2 show the amount of growth of the underlying nickel layer, that is, the amount of increase of the underlying nickel layer by performing the covering nickel plating after performing the plating to form the underlying nickel layer.

In this way, in the embodiment of the present application, when the deposition amounts of the underlying nickel layer and the roughened plating layer are obtained from the cross-sectional photographs of the scanning electron microscope, the deposition amounts (thicknesses) of the respective layers can be calculated by using 2.8 g / m ² ( Amount corresponding to 0.32 µm) can be subtracted from the underlying nickel layer and added to the roughened plating layer.

<< Example 42 >>

After the underlying nickel layer was formed on both sides of the steel sheet under the same conditions as in Example 1, one side of the steel sheet on which the underlying nickel layer was formed was masked and the electrolytic plating became on the opposite side of the masked side using the plating bath for roughened nickel having the same bath composition as in Example 1 under the same conditions as in Example 1, whereby nickel grains were precipitated on the underlying nickel layer. Further, by performing electrolytic plating under the same conditions as in Example 1 using covering nickel plating bath was carried out with the same bath composition as in Example 1, covering nickel plating, whereby a roughened, nickel-plated sheet (a roughened, nickel-plated sheet of the in 1B embodiment shown) in which the roughened nickel layer was formed on only one surface. The roughened nickel-plated sheet thus obtained was evaluated in the same manner as in Example 1, and it was confirmed that the same shape and effects were obtained.

List of reference symbols

1, 1a

roughened, nickel-plated sheet metal

11

Metal base material

12th

Roughened nickel layer

121

Nickel grains

122

Nickel film

13th

Metal plating layer underneath

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• JP 5885345 [0004]

Claims (6)

Roughened, nickel-plated sheet metal with a roughened nickel layer as the outermost surface layer on at least one surface of a metal base material, wherein the brightness L * of the surface of the roughened nickel layer is 30 to 50, the gloss level of 85 ° of the surface of the roughened nickel layer is 1.5 to 50. Roughened, nickel-plated sheet metal Claim 1 wherein the metal base material is a metal sheet or a metal foil made of a kind of pure metal selected from Fe, Cu, Al and Ni, or a metal sheet or a metal foil made of an alloy which is a kind selected from Fe, Cu, Al and Ni, contains is. Roughened, nickel-plated sheet metal Claim 1 or 2 wherein the metal base material is a steel sheet. Roughened, nickel-plated sheet metal according to one of the Claims 1 to 3 wherein the thickness of the metal base material is 0.01 to 2.0 mm. Roughened, nickel-plated sheet metal according to one of the Claims 1 to 4th , the deposition amount of nickel plating being 5.0 to 50.0 g / m ^2. Roughened, nickel-plated sheet metal according to one of the Claims 1 to 3 wherein the roughened nickel layer has an arithmetic mean roughness Ra of 0.1 to 3.0 µm by laser microscopy and the roughened nickel layer has a ten-point mean roughness Rz _jis of 2.0 to 20.0 µm by laser microscopy.

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